Food Reviews International

This article was downloaded by: [Pennsylvania State University]
On: 28 April 2013, At: 22:29

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Food Reviews International

Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/lfri20
Solubility of Carotenoids in Supercritical

CO2
a b b a
John Shi , Gauri Mittal , Erin Kim & Sophia Jun Xue
a
Guelph Food Research Center, Agriculture and Agri-Food Canada,
Ontario, Canada
b
School of Engineering, University of Guelph, Ontario, Canada
Version of record first published: 21 Sep 2007.
To cite this article: John Shi , Gauri Mittal , Erin Kim & Sophia Jun Xue (2007): Solubility of
Carotenoids in Supercritical CO2 , Food Reviews International, 23:4, 341-371
To link to this article: http://dx.doi.org/10.1080/87559120701593806
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation
that the contents will be complete or accurate or up to date. The accuracy of any
instructions, formulae, and drug doses should be independently verified with primary
sources. The publisher shall not be liable for any loss, actions, claims, proceedings,
demand, or costs or damages whatsoever or howsoever caused arising directly or
indirectly in connection with or arising out of the use of this material.
Food Reviews International, 23:341–371, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 8755-9129 print / 1525-6103 online
DOI: 10.1080/87559120701593806
Solubility of Carotenoids in Supercritical CO2

1525-6103
8755-9129
LFRI
Food Reviews International
International, Vol. 23, No. 4, August 2007: pp. 1–56
JOHN SHI1, GAURI MITTAL2, ERIN KIM2 AND

Solubility
Shi et al. of Carotenoids
SOPHIA JUN XUE1

1
Guelph Food Research Center, Agriculture and Agri-Food Canada, Ontario,
Canada
2
School of Engineering, University of Guelph, Ontario, Canada
Downloaded by [Pennsylvania State University] at 22:29 28 April 2013
Carotenoids have been shown to provide a range of health benefits and to decrease the
risk of disease. Although carotenoids are naturally present in plants advanced extraction
technologies to remove carotenoids from plant materials are needed to prepare concen-
trated materials. Because carotenoids are sensitive to heat, oxygen, and light, large-scale
supercritical fluid extraction (SFE) has drawn attention as a separation technology. SFE
with solvents such as CO2 offers an organic-chemical-free process that yields quality end
food products, compared to traditional extraction methods that organic solvents. In the
SFE process for plant materials, an important step is to measure and predict the solubility
of target components in the supercritical fluid at various pressure and temperature condi-
tions to optimize the extraction process. The solubility of targeted carotenoids in super-
critical fluids is related to its physical and chemical properties such as polarity, molecular
structure, and nature of the material particles, and it is also related to the operating con-
ditions such as temperature, pressure, density of solvent and co-solvents, and solvent flow
rate in the supercritical region. The solubility of b-carotene, a-carotene, and other caro-
tenoids under different extraction conditions has been reviewed. It would be interesting
and useful for researchers and food industries to compare the data of the solubility of car-
otenoids to develop optimum extraction process and to get maximum yields.
Keywords cartenoids, extraction, supercritical fluid, solubility
Introduction
A growing interest and demand for healthy, environmentally safe, and cost-efficient products
has driven the research and application of new technologies in the food, pharmaceutical, and
cosmetic industries. Extraction processes are commonly used to enrich and detoxify food
through the removal of targeted components from natural products. Organic solvents have
been a popular choice in the extraction of biomolecules such as carotenoids from plant mate-
rials. However, alternative and reliable extraction techniques have been of great interest
because organic solvents are costly, environmentally hazardous, and require expensive dis-
posal procedures.(1) While there are a great number of different extraction methods, including
chromatography, solid-liquid extraction, precipitation, and ion exchange, there has been a
growing interest in supercritical fluid extraction (SFE) for large-scale production industries.(2)
A major difficulty in utilizing SFE for biomolecules is to measure and predict their solubility
in supercritical solvents at various pressure and temperatures for process optimization. Lack
of data for intermolecular energy parameters, critical properties, and molecular refraction lim-
its the use of modeling for prediction of their solubility in supercritical solvents.(3)
Address correspondence to John Shi, Guelph Food Research Center, Agriculture and Agri-
Food Canada, Ontario, Canada. E-mail: shij@agr.gc.ca
341
342 Shi et al.
When a fluid is subjected to conditions that exceed supercritical temperature and pres-
sure, it is referred to as a supercritical fluid. When the fluid enters this phase, it adopts an
array of gas and liquid properties, as well an increased solvent capacity and parameter sensi-
tivity. A series of commonly used supercritical solvents and their respective critical points
are listed in Table 1. The critical temperature and critical pressure are characterized by the
point in which phase transition is no longer possible, regardless of changes in pressure.
Physical characteristics, including diffusivity, viscosity, and surface tension attribute to the
increased solvent capacity of the fluid, which may be exploited for extraction applications.(4)
Supercritical fluids have many unique and valuable properties that make them ideal
agents in the pharmaceutical, nutraceutical, food, and cosmetic industries. Nontoxicity is a
major advantage, because fluids such as carbon dioxide and water may be used in pro-
cesses that would otherwise require toxic organic solvents for extraction.(5) A solvent-free
product may be obtained by extracting a solute at the supercritical condition of the solvent
and reducing the temperature and pressure below this point to separate the solute from the
solvent. This is possible since a sudden temperature or pressure reduction typically causes
a loss in solvent power because of the solvent sensitivity to these parameters. The super-
critical fluid may be recovered and used again, thus saving costs.(3)
The solvation power (dissolving capacity) of supercritical fluids is sensitive to the
temperature and pressure changes in the supercritical region; therefore, it may be finely
adjusted according to particular needs. This is one of the primary characteristics of super-
critical fluids that make them an attractive agent. Temperature and pressure can affect the
equilibrium solubility by two or three orders of magnitude.(5) Rapid extraction and phase
separation are possible because supercritical fluids have high mass diffusivity and low
viscosity.(3) Sensitivity to these parameters provides an opportunity to fine-tune the condi-
tions to optimize the results. In addition, SFE is a relatively energy efficient process.(6)
Supercritical fluid extraction is ideal in the food and pharmaceutical industries
because solvents such as CO2 have low critical temperatures, thus facilitating and optimiz-
ing the extraction of thermally unstable compounds.(3) An example is the extraction of
β-carotene, which may be obtained without degradation from its relatively low supercriti-
cal temperature.(7) Other applications of SFE include the decaffeination of green coffee
beans, removing nicotine from tobacco leaves, and the dehydration of organic solvents.(6)
Table 1
Critical properties of commonly used supercritical fluids(1–6)
Molecular weight Critical Critical pressure
Fluid (g/mol) temperature (K) (MPa)
Carbon dioxide 44.01 304.1 7.38
Water 18.02 647.3 22.12
Methane 16.04 190.4 4.60
Ethane 30.07 305.3 4.87
Propane 44.09 369.8 4.25
Ethylene 28.05 282.4 5.04
Propylene 42.08 364.9 4.60
Methanol 32.04 512.6 8.09
Ethanol 46.07 513.9 6.14
Acetone 58.08 508.1 4.70
Solubility of Carotenoids 343
Supercritical Fluid Extraction

The organic solvents acetone and other hydrocarbons may be used in the extraction of nat-
ural components from plant material. However, many of these solvents are toxic and must
be removed with processes such as distillation or evaporation, often under reduced pres-
sure. Processes that apply the use of organic solvents may require highly flammable liq-
uids and the final product may contain harmful residues despite postprocessing to remove
particular chemicals. The product may be unfit for human consumption because of con-
tamination. In the food industry in particular, as consumers become increasingly aware of
the dangers of chemical residues, there is a corresponding increase in the demand for safe
and cost-efficient techniques.(8) Environmental contamination is reduced through the use
of SFE, since fluids such as CO2 can be safely collected and recycled, unlike organic sol-
vents. In addition, such traditional methods are often complicated by the degradation and
isomerization of the targeted biomolecules because of heat, light, and oxygen exposure.(9)
Thus, the application of SFE for the extraction of biomolecules has become an ideal alter-
native to organic solvents. Although CO2 is typically a nonpolar poor solvent, an increase
in pressure causes an increase of density, which substantially improves its dissolving
capacity.(2) Supercritical fluid extraction is an ideal extraction method for labile biomole-
cules such as carotenoids since it may operate at relatively low temperatures and pres-
sures. A schematic of a typical SFE apparatus is shown in Fig. 1.
Although the application of supercritical fluid extraction may produce yields that are
significantly lower than methods that use organic solvents, with the exception of hydro-
carbons and sulfur-dioxide, the hazard and cost issues that accompany organic solvent
extraction pose significant drawbacks. In addition, there is evidence of chemical reactivity
with some organic solvents with commonly targeted compounds such as β-carotene.(8)
Common Supercritical Fluids Used in Supercritical Fluid Extraction

The solubility of carotenoids is also dependent on the type of fluid used for the process.
The molecular weight, polarity, critical parameters and polarizability affect the solubility
of different components in the extraction process. For example, the solubility of β-
carotene is higher in fluids that have greater molar polarizability and are nonpolar. Ethane
and carbon dioxide are both nonpolar fluids; however, ethane is a better solvent because of
its greater polarizability and will yield solubilities and order of magnitude higher in terms
of mole fraction.(10) Xenon also has a higher polarizability; however, high costs limit its
use in large-scale operations.(8) Bonding should also be taken into account when assessing
Carbon Dioxide
Low Pump Release
Pressure Extractor
Heat Exchanger
Cooling
Separator
Bath
High
Carbon Dioxide Pressure Product Release
Source Heat Exchanger
Figure 1. Typical experimental apparatus used to measure solubilities in supercritical fluids.

344 Shi et al.
the solubility of carotenoids in supercritical fluids. Despite being relatively high in polar-
izability, β-carotene was found to be completely insoluble in SC-SF6, possibly due to the
high ionic character of the S-F bonds.(8)
Carbon Dioxide. Carbon dioxide is a common solvent because it is nontoxic, inexpen-

sive, easy to obtain with high purity, nonflammable, easily separable, and has a relatively
low critical temperature.(5,11) A phase diagram of SC-CO2 is shown in Fig. 2. The critical
temperature is easy to reach since it is relatively close to room temperature and it is an
ideal solvent for thermally labile compounds such as carotenoids. The lack of residues
from SFE processes is another advantage that this process provides in the food industry.(1)
Supercritical carbon dioxide (SC-CO2) may be applied in the extraction process at rela-
tively low pressures and temperatures without sacrificing compound stability or integ-
rity.(12) An issue found with SC-CO2 is the nonpolarity of the solvent; however, this may
be solved through the addition of a small amount of polar modifiers.(1)

A problem that may occur when using SC-CO2 in carotenoid processing is that there
is a small amount of oxygen always present in commercial CO2. Carotenoids may react
with the oxygen, resulting in degradation. This effect suggests that an analysis of the prod-
ucts should be performed to ensure that a significant amount of carotenoid degradation did
not occur as a result of the pigments coming in contact with SC-CO2.
Water. Supercritical water (SC-H2O) may be used for the destruction of organic com-
pounds, which is useful for the treatment of hazardous organic waste and coal and crude
oil processing. Supercritical water oxidation (SCWO) can effectively and completely
decompose organic waste material into safer compounds such as water and carbon dioxide.
This is because above the critical point, oxygen and organic compounds can be quickly
reacted in a single phase because both are soluble. Other organic compounds such as chlo-
rine or sulfur may be oxidized to become inorganic compounds that can be neutralized and
disposed.(13) Relative to ambient conditions, organic solubility increases while salt solu-
bility decreases at supercritical conditions for water. Economically, SCWO is an attractive
process for waste treatment processes, and water has also been used at subcritical temper-
atures. However, Savage et al.(14) noted a number of advantages for using water in the
Supercritical
Region
Liquid phase
Pressure (MPa)
PC
Solid Phase
Triple Gas Phase

Tc = 31.1°C
Point
Pc = 7.38 MPa
TC
Temperature (°C)
Figure 2. Supercritical pressure-temperature diagram for carbon dioxide. Tc and Pc denote critical
temperature and critical pressure, respectively.
supercritical state. First, the reaction rates are higher because of the high temperature. Sec-
ond, organics, water, and an oxidant may exist in a single phase because of the unique
properties of supercritical fluids, while processes that operate at subcritical conditions
usually involve multiphase systems that limit oxidation rates. Last, spreads the fact that
salts that are less soluble in SC-H2O allows them to precipitate from the solution, which
may be used to purify the effluent stream.(15)
Water is also used in a subcritical state in a process called pressurized low polarity
water (PLPW). The solvent is kept in a liquid form, with high pressure at a temperature
significantly above the atmospheric boiling point. Its chemical properties become similar
to those of organic solvents. Benefits of using PLPW for extraction include reducing the
use of organic solvents, increasing the efficiency of extraction process, speed, relatively
high selectivity, cleanliness, and cost savings of both raw material and energy.(16) In a
study comparing SC-CO2 and subcritical water extraction, Clifford et al.(17) found that
although the yield of the oil from the samples was very similar, certain compounds were
more soluble in subcritical water than SC-CO2. It was also noted that while both SFE and
PLPW are controlled by partitioning between the plant matrix and solvent, the rate of sol-
vation for SFE is also influenced by the transportation of the molecules out of the plant
matrix.
Alcohol. The literature on supercritical alcohol extraction is relatively limited. Supercriti-

cal alcohol has been used in the preparation of biodiesel.(18) The liquefaction of food wastes
such as olive husks and hazelnut shells can be performed and SFE can be applied to obtain
oil products for manufacturing synthetic fuels.(19) However, Table 1 shows that alcohols
such as methanol and ethanol have a much higher supercritical temperature than SC-CO2
and therefore, may not be suitable solvents for the extraction of certain components.
The structure of supercritical alcohol has less order than when it is in a liquid state.(20)
It was also found that the percentage of hydrogen bonds decreased as the temperature rose,
although some hydrogen bonds still exist in the supercritical region. Hydrogen bonding is
an important parameter, since the nature of fluid interactions influences the properties of
associating fluids. In addition, hydrogen bonding is the most temperature sensitive to the
Hansen solubility parameters because bonds are progressively broken as the temperature
is increased, thus causing a rapid decrease in these parameters at higher temperatures.
Postprocessing treatment that is required after using supercritical alcohols is rela-
tively simple; therefore, solvents such as supercritical 2-propanol are ideal for some pro-
cesses. Since no reagents are required, removal simply consists of the 2-propanol and the
acetone produced by evaporation.(21)
In addition to serving as a reactant, supercritical alcohol acts as an acid catalyst. The
reactivity of the alcohol is greater for molecules with shorter chains, which agrees with a
reaction rate comparison between methanol, ethanol, 1-propanol, 1-butanol, and
1-octanol. This is due to the decreased alcohol acidity that occurs with alcohols with long
alkyl chains.(18)
Ethane. Ethane (C2H6) is also considered to be an acceptable solvent for food products,
and has a critical temperature close to that of CO2 (305.3°K). It is more expensive than
CO2; however, ethane’s lower critical temperature may offset its higher cost depending on
the nature of the extraction. Certain solutes such as cholesterol and citrus oils have lower
ethane consumption due to higher solubilities, and reduced operating costs due to the
lower operating pressures and extraction times. Using ethane is more economically viable
than carbon dioxide for cholesterol extraction, despite the fact that the price of obtaining
346 Shi et al.
ethane is approximately twice as much as carbon dioxide.(22) Ethane systems have higher
solubility differences and are less temperature dependent than their carbon dioxide coun-
terparts; therefore, it may be easier to optimize the operating conditions in terms of both
separation selectivity and extraction yield.(23)
Solubility of Carotenoids in Supercritical Fluids

Solubility refers to the amount of solute that will dissolve in a given amount of solution at
thermodynamic equilibrium. In other words, it is the upper limit that the solvent can hold,
when it becomes saturated. Interactions between solvent and solute molecules influence
the tendency of a particular substance to dissolve in a solvent. Ideally, the intermolecular
forces of a solvent should match that of the targeted compound for optimal solubility. For
example, β-carotene, a precursor of vitamin A shows a large region containing only non-
polar C-C and C-H bonds (Fig. 3); thus, there are very few hydrogen bonding sites, ren-
dering if insoluble in water.(24)
To predict the compatibility of various solvents and solutes, solubility parameters
have been developed to forecast miscibility and solvation. Hansen(25) developed solubility
parameters based on the principle of total energy of vaporization of a liquid as influenced
by dispersion forces, permanent dipole forces, and hydrogen bonding. When the Hansen
solubility parameters (HSP) for materials are similar, they are more likely to be combined
in a reaction. The extent of this affinity is determined by the degree of similarity.
Hanson(25) also noted that elevating the temperature generally leads to an increase in solu-
bility. The hydrogen bonding parameter is more sensitive to temperature than the polar
solubility or the dispersion solubility parameters.
In SFE processes, the size and shape of the molecules also affects solubility, perme-
ation, diffusion, and chemical resistance phenomena. Small and uniform molecules are
ideal, because they typically have higher solubility and more rapid diffusion.(25) The solu-
bility behavior of many compounds is exploited in SFE, because a sudden decrease in
temperature will typically reduce solubility. After the solute has dissolved in the solvent, a
solution exists that contains both the supercritical fluid and a solute component. By
rapidly decreasing the temperature, the solute separates after as a solid, and this can be
collected.
The solubility of targeted compounds is important when establishing the extraction
parameters. To obtain the maximum amount of yield from a source material, the solubility
of a component in the solvent should be as high as possible. It also dictates the amount of
solvent necessary to optimize the efficiency.
Properties of Targeted Components in Supercritical Fluid Extraction

The nature of the targeted molecules in an extraction process dictates the optimal choice for
its corresponding solvent. In the case of SC-CO2, nonpolar lipophilic solutes experience high
Figure 3. Structure of β-carotene.

extractability; however, the existence of polar functional groups impedes solubilitation.(26)

This is not the case for all supercritical fluids because of various chemical and physical
properties. Supercritical ethane (SC-C2H6) is a better choice for simple aromatic hydrocar-
bons, while fluoroform works well with molecules that contain potential hydrogen bond-
ing sites.(27) The solubility of multicomponent solute systems is dependent on the
solubility of the individual proportions. Solubility of ternary systems has been found to be
higher than pure solid systems at the same operating conditions.(6) In the case of hydrocar-
bons, carboxylic acids, and alcohols in SC-CO2, as the carbon chain of the solute
increases, the solvent power of SC-CO2 decreases. Although the same behavior occurs for
alkanes and alkenes, the latter experiences higher solubility. Methyl branches, however,
have favorable effects on solubility. Other structural qualities that should be taken into
account include branches, rings, substituents, aromaticity, and acidity.(28) Although the
structure of the compound influences the solubility, an advantage that SCF provides is the
ability to dissolve components of similar volatility, despite dissimilar molecular organiza-

tion. Although compounds with high molecular weight are typically nonvolatile, adjust-
ments may be made to increase the pressure of the system to compensate for this issue.(26)
Typical Behavior of a Solid Solute in a Supercritical Solvent

The extraction of natural products using supercritical fluids typically occurs in three dis-
tinct phases.(29,30,31) Initially, there is a constant extraction rate period, a falling rate
period, and a diffusion-controlled rate period. The constant rate period likely occurs
because components that are easily transferred from the solid to fluid phase such as oil are
situated near the surface of the particles. Samples are often ground before extraction, rup-
turing cells and causing oil to cover the surface of the resultant particles. Therefore, the
mass transfer during the constant extraction rate period is mostly between the oil that is
covering the particles and the solvent, until solubility limits are reached.(31) The falling
extraction rate period is influenced by diffusion in the solid phase.(32) A combination of
the solvent’s ability to diffuse through the solid and back-diffusion of any dissolved com-
ponents to the surface characterize this phase of the extraction process, as well as interac-
tions of readily available components that are still on the particle surface.(31) After these
components are removed, the diffusion controlled period commences. Particles found
deeper within the solid particles now can be obtained because of the absence of the com-
ponents that controlled the mass transfer rates during the first two phases.
This typical behavior is observed in the extraction of buriti fruit in Fig. 4, along with
the increase in solvating power at an elevated pressure. Results at 20 MPa and 30 MPa
indicated that as the pressure increases, the slope of the constant extraction rate period
increases, corresponding to the rise in solute solubility for the components at the surface
of the particles that are dissolved rapidly because of the increase in solvation power.(30)
Components that are readily available on the surface of the particles such as lipids and oils
are relatively less energy intensive to remove than compounds that are found deep within
the particles, such as β-carotene. This is because the yield obtained in the latter part of the
extraction does not eclipse the drastic increase in the necessary solvent compression
costs.(30)
Carotenoids
Pigments are widely used in the food industry, and color is a significant factor for the deter-
mination of freshness and quality, consumer acceptability, identification, and marketability
348 Shi et al.
7
Amount of Oil (g)
3
20 MPa
2 30 MPa
0
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Amount of CO2 (g)
Figure 4. Extraction data of buriti fruit at 313 K and pressures of 20 and 30 MPa. (Modified from
de França et al.(30) with permission from Elsevier).
of many products. Carotenoid pigments are natural coloring agents that are typically
extracted from seeds, fruits, flower petals, and so on for the food, cosmetic, and pharma-
ceutical industries. These antioxidants play a vital role in the human body(12) and are the
main source of vitamin A for humans. Common carotenoid applications include animal
feed, cosmetic products, and natural colorants for food products such as salad dressing and
popcorn.(33) In nature, the main sources of carotenoid pigments are paprika and carrots;
however, synthetic carotenoids such as β-carotene are produced because of high consumer
demand(12) fuelled by evidence that antioxidants reduce cardiovascular disease and can-
cer.(34) However, concerns of contamination during synthetic carotenoid production idealize
the extraction of naturally occurring carotenoids with supercritical fluids.(12) In addition to
safety and tolerance concerns, synthetic carotenoids typically undergo mutagenic, carcino-
genic, and pathogenic evaluation because of pharmacological scrutiny.(4)
Demanding regulations about the application of artificial dyes and synthetic additives
have spurred the increasing use of carotenoids in the food industry.(35) Consumer interest
in carotenoids has recently grown because of evidence of health benefits such as antitu-
mour activity.(36) In addition, unlike many other dyes, the presence of ascorbic acid or
heating and freezing cycles do not affect carotenoid activity. Even in small amounts, caro-
tenoids are able to provide the desired qualities making certain carotenoids very desirable
dyes for many food products.(35)
To ensure maximum yields, mild conditions should be applied in the extraction for
carotenoids from natural sources. Excessive exposure to heat and light may lead to the
isomerization and decomposition of carotenes.(12) Cis-trans isomerization reactions of car-
otenoids have been reported at room temperature and with exclusion of light, which causes
a partial loss of provitamin A activity.(37) Conversion of all-trans β-carotene to stereo-
isomers is undesirable because of the relatively low biological activity that accompanies
cis-isomers.(38) In addition, cis-isomers that result from the conversion of all-trans-lycopene
are less colored and are more oxidizable.(39) The structures of these compounds break down,
thus eliminating all nutritional, medical, and colorant properties under light exposure at
room temperature. Sources of carotenoids that have been used in supercritical fluid extrac-
tion include tomatoes, buriti fruit, carrots, microalgae, and paprika.(30,40–44)
Carotene. β-carotene (C40H56) is a relatively nonvolatile compound,(36) has no functional

groups, and represents a hydrophobic natural product.(45) This nonpolar compound is
widely distributed in plant and animal tissues, and has been extracted from natural prod-
ucts such as carrots, algae, and palm oil.(11) It is a yellow to dark red pigment that is lipid
soluble, and is easily degradable by light, heat, and air. It has a high molar mass and an
elongated shape, which possibly explains why the solubility of this carotenoid in SC-CO2
is much lower than in other fat-soluble vitamins.(5)
There is great consumer interest in β-carotene bioavailability in food products since it
exhibits high provitamin A activity(12) and has been noted for its nutritional functions and
its anticancer properties.(46) Desirable traits such as uniform color and vitamin A activity
may be obtained through the addition of β-carotene to food products.(47) The nutritional,
pharmacological, and colorant functionalities of carotenoids make them components of
great interest in the food technology field.(9)
In the process of extracting carotene from carotene-rich material such as carrots and
tomatoes in SFE, carotene is mainly obtained in the diffusion-controlled extraction period.
This results in relatively higher costs than the extraction of some other components, such
as fat-soluble compounds, because of the higher energy and material demand. When such
fat-soluble components are targeted, there is no need to complete the entire extraction pro-
cess because high-solvent compression costs make it cost-inefficient. In carotene, how-
ever, a high concentration is not obtained until the lipids that are in or near the surface are
dissolved in the SC-CO2. After this point, a product with a higher carotenoid concentra-
tion may be obtained.(30)
The molecular weight of β-carotene is relatively large (536.88 g/mol), which is a
factor known to inhibit the solubility of solutes in supercritical fluids.(28) Tables 2a and b
are literature data concerning the solubility of α-carotene and β-carotene in supercritical
fluids with various parameters. It has been suggested that β-carotene reacts with oxidiz-
ers such as SC-CO2 since it is a strong reducer, although there is some discrepancy in the
literature. β-carotene is a long chain material with weak Van-Der-Waals molecular
forces; a study conducted by Chang and Randolph(36) found a β-carotene–related epoxide
compound produced from a reaction between the carotenoid and the CO2. However,
results from Jay et al.(48) showed no evidence of carotenoid oxidation. In addition, Coc-
ero et al.(49) stated that from a chemical viewpoint, a chemical reaction between β-
carotene and carbon dioxide is impossible.
Lycopene. Tomatoes and tomato products are major sources of lycopene (C40H56), an
antioxidant that has been thought to prevent cancer, heart disease,(1) and atherosclerosis.(50)
The structure of lycopene is shown in Fig. 5. Concentrations of this carotenoid in tomatoes
can be as high as 50 mg/kg, and it has higher color intensity than β-carotene.(51) Other
sources of lycopene include pink grapefruit, guava, watermelon, and apricots.(52) Tomato
skin constitutes approximately five times more lycopene than the pulp; however, the seeds
and skins are often discarded in the tomato processing industry as waste, and its use is
essentially limited to animal feed.(33) Therefore, the skins and seeds from tomatoes that
normally go to waste are ideal agents for lycopene production, although seeds do not con-
tribute as much to the carotenoid content. In fact, a study conducted by Sabio et al.(33)
found that the lycopene extraction yields were higher in samples that consisted of tomato
skin than samples with a combination of skin and seeds.
Table 2a
Compilation of literature data for α-carotene solubility and yield in supercritical fluids from various sources
Yield Pressure CO2 flow rate
SCF Solid material Cosolvent(s) (g/g raw material) ×106 Temp (K) (MPa) (m3/h) ×103 Reference
CO2 carrot powder CO2 82.2 313 40.4 30–36 (12)
5% hexane + CO2 92.7 313 60.6 48–51 (12)
5% chloroform + CO2 111.2 313 60.6 42–48 (12)
CO2 carrots, ground and dried CO2 + 5% ethanol 215a 303 3 – (41)
300a 323 3 – (41)
350
CO2 + 10% ethanol 250a 303 3 – (41)
605a 323 3 – (41)
CO2 carrot, freeze dried and ground CO2 181.7 313 27.6 60 (55)
328.6 343 27.6 60 (55)
CO2 + 2.5% (w/w) canola oil 369.1 313 27.6 60 (55)
607.3 343 27.6 60 (55)
CO2 + 5% (w/w) canola oil 443 313 27.6 60 (55)
550.9 343 27.6 60 (55)
– not reported.
Table 2b
Compilation of literature data for β-carotene solubility and yield in supercritical fluids from various sources
Yield (g/g raw Solubility (g/g Temp Pressure Density
SCF Solid material Co-solvent(s) material) ×106 solvent) ×106 (K) (MPa) (kg/m3) Reference
CO2 crystalline synthetic CO2 – 1.6 298 21 921.2 (7)
trans-β-carotene, 95% purity – 5.5 313 25.7 884.7 (7)
N2O β-carotene, 97% purity – 6 288 5.1b 880 (8)
– 22.6 313 20 841 (8)
C2H6 β-carotene, 97% purity – 13.4 288 25 452 (8)
– 28.9 308 35 449 (8)
C2H4 β-carotene, 97% purity – 9.2 308 20 384 (8)
– 101.2 328 50 442 (8)
Xe β-carotene, 97% purity – 59 300 27.3 2270 (8)
– 118.4 329 29.6 2090 (8)
351
SF6 β-carotene, 97% purity – 0.01 323 35 1800 (8)
C3H8 β-carotene, 97% purity – 79.3 288 7.3b 510 (8)
CHClF2 β-carotene, 97% purity – 31.3 288 8.0b 1231 (8)
NH3 β-carotene, 97% purity – 0 288 7.3b 700 (8)
CCl2F2 β-carotene, 97% purity – 41.7 288 4.8b 1345 (8)
n-C4H10 β-carotene, 97% purity – 108.7 288 1.5b 570 (8)
CO2 β-carotene standard, 95% purity CO2 – 2.6 313 27.6 897.1 (10)
– 6.3 323 29.9 870.7 (10)
– 7.7 333 27.4 805.1 (10)
CO2 carrot powder CO2 – – 313 40.4 – (12)
5% hexane + CO2 – – 313 60.6 – (12)
5% chloroform + CO2 – – 313 60.6 – (12)
(Continued)
Table 2b
(Continued)
C2H4 trans-β-carotene CO2 – 181.8 323 10.3 – (14)
– 784.7 343 17.2 – (14)
0.70% Toluene + CO2 – 2890.2 343 31 – (14)
1.85% Toluene + CO2 – 6871.3 343 31 – (14)
2.07% Toluene + CO2 – 7177.5 343 31 – (14)
2.18% Toluene + CO2 – 6986.1 343 31 – (14)
2.36% Toluene + CO2 – 22355.6 343 37.9 – (14)
CO2 buriti shell and pulp oil CO2 – 8.9a 313 20 – (30)
CO2 synthetic trans-β-carotene, 97% CO2 – 0.4 313.2 12 718.9 (32)
352
purity – 2.8 333.2 20 724.5 (32)
CO2 + ethanol – 6 313.2 15 – (32)
– 17.1 333.2 28 – (32)
CO2 + vegetable oil – 2.8 313.2 20 – (32)
– 9.1 333.2 28.3 – (32)
CO2 tomato paste waste, dried and CO2 100.9 – 308 30 – (40)
ground 103.8 – 338 30 – (40)
CO2 + 5% ethanol 114.8 – 308 30 – (40)
154.7 – 338 30 – (40)
CO2 + 10% ethanol 115.5 – 308 30 – (40)
145.5 – 338 30 – (40)
CO2 + 15% ethanol 120.6 – 308 30 – (40)
104.9 – 338 30 – (40)
CO2 carrots, ground and dried CO2 + 5% ethanol 150a – 303 3 – (41)
197a – 323 5.1 – (41)
CO2 + 10% ethanol 193a – 303 3 – (41)

225a – 323 5.1 – (41)
CO2 β-carotene standard from carrots CO2 – 0.02a 313 6.8 190a (45)
– 28.1a 343 33.3 815a (45)
CO2 β-carotene standard, 95% purity CO2 – 0.3 308 10 700 (46)
– 6.1 323 29.5 867 (46)
CO2 β-carotene standard, 95% purity CO2 – 1.1 313 20 840.2 (47)
– 39.5 353 32 788.9 (47)
CO2 β-carotene standard, 98% purity CO2 – 1.9 313 30 910 (49)
– 8 333 30 830 (49)
CO2 tomato seeds and skin, dried and CO2 154.5 – 313 27.6 – (53)
ground 348.8 – 353 27.6 – (53)
CO2 β-carotene standard and CO2 – 0.2 310 9.7 673 (54)
synthetic β-carotene – 20.7 340 26 756 (54)
CO2 carrot, freeze dried and ground CO2 220.3 – 313 27.6 – (55)
353
386.6 – 343 27.6 – (55)
CO2 carrot, freeze dried and ground CO2 + 2.5% (w/w) 387.1 – 313 27.6 – (55)
canola oil 755.7 – 343 55.1 – (55)
CO2 carrot, freeze dried and ground CO2 + 5% (w/w) 481.3 – 313 27.6 – (55)
canola oil 868.1 – 343 41.3 – (55)
CO2 β-carotene standard CO2 – 5.3 313 12 – (56)
– 11.5 323 20 – (56)
CO2 carrots, dried and ground CO2 – 0.3 313 12 – (56)
2.9 323 20 – (56)
CO2 pure crystalline β-carotene CO2 – 23.3 343 40 853.8 (60)
CO2 + 1 wt.% ethanol – 11.7 343 22.3 700.6 (60)
(Continued)
Table 2b
(Continued)
CO2 + 1 wt.% – 15.6 343 23.4 716.5 (60)
methylene chloride
CO2 + 1 wt.% – 4.9 343 18 612.6 (60)
methanol
CO2 trans-β-carotene vegetable oil CO2 – 11.8 333 30 – (67)
(14.8% w/w)
CO2 paprika oleoresin CO2 – 0.7 333 30 – (67)
CO2 red pepper flakes, ground and CO2 640 – 313 32 922 (70)
dried 690 – 313 54 1005 (70)
CO2 ground paprika CO2 57 – 308 20 – (71)
354
454 – 308 40 – (71)
CO2 all trans-β-carotene synthetic, CO2 – 0.1 307.6 8 490.9 (72)
amorphous, purity 97% – 5.3 322.9 60 994.5 (72)
CCIF3 all trans-β-carotene synthetic, CCIF3 – 0.4 308.9 120 1584.2 (72)
amorphous, purity 97% – 1.8 326 180 1653.3 (72)
CO2 all-trans β-carotene, purity 97.1% CO2 – 0.2 288 5b 825 (73)
– 15.9 308 50 949 (73)
N2O synthetic, crystalline all-trans N2O – 2.3 307.6 8 693.4 (75)
β-carotene – 7.8 315 15 774.5 (75)
N2O synthetic, crystalline all-trans N2O – 8.6 322.9 15 731.1 (75)
β-carotene
a
Values estimated from graph.
b
Saturated vapor pressure of liquid.
– not reported.
Figure 5. Structure of lycopene.
This carotenoid accounts for approximately 80–90% of the pigment content in ripe
tomatoes, and is prone to degradation from exposure to light, heat, and oxygen.(50) About
72–92% of the pigments in tomatoes are found in the water insoluble fraction and the skin
of tomatoes.(52) The insolubility of lycopene in water causes an issue when attempting to
extract it from natural products. Although it is soluble in organic solvents such as benzene,
chloroform, and methylene chloride, these are toxic and are therefore not ideal candidates
for pharmaceutical, food, or cosmetic purposes. This is one of the main reasons why lyco-
pene solubility in supercritical fluids has become of great interest.(53) However, informa-
tion concerning the supercritical extraction of lycopene is not easily available and there
are many areas that have yet to be thoroughly explored.(50) While β-carotene extraction
with supercritical fluids has been explored, interest in isolating lycopene with SFE has
surfaced only within the past decade. Like β-carotene, lycopene is seen as a valuable
compound for the pharmaceutical, nutrition, and feed industries as a natural colorant with
anticancer properties.(50)
Lycopene content in plant materials is dependent on the species and the temperature
at which growth and maturation occurs. Factors such as climate trends significantly alter
the amount of lycopene in the material, thus affecting the yield. Lycopene is the last pig-
ment to appear during maturation, and its development is inhibited by temperatures higher
than 30–32°C, while other carotenoids degrade at these temperatures. As a result, the pig-
ment concentrations in plant materials may vary between crop cycles.(53) Lycopene yield
and solubility data from the literature are given in Table 3. Extraction temperatures vary
from 308 K to 359 K and pressure from 17.1 MPa to 48.28 MPa.
Factors Affecting the Solubility of Carotenoids in SFE

There are numerous factors that affect the solubility of carotenoids in supercritical fluids.
As previously discussed, the solvating power of fluids in the supercritical phase is very
sensitive to changes in temperature and pressure. However, other parameters, including
the flow rate of the fluid, the presence of co-solvents and modifiers, storage conditions,
extraction times, moisture content of the samples, and compound morphology, should also
be considered. In addition, one must be cautious when dealing with labile compounds that
may degrade or isomerize when parameters reach or exceed certain thresholds. A compila-
tion of studies investigating the solubility of carotenoids in supercritical fluids is presented
in Tables 2 to 11. Discrepancies may arise from numerous factors, including sample impu-
rities, different analytical approaches, and a lack of uniformity in sample preparation. The
section on Pressure through Water Content of the Material discusses how various factors
affect the solubility and yield of carotenoids from supercritical fluid extraction.
Pressure. An increase in pressure at a constant temperature increases the solvating power

of the SCF. This results in an increase in solvent density and allows extraction of a wider
variety of carotenoids. Data from Johannsen and Brunner(47) demonstrated that solvating
power of fluids such as CO2 increases as the density increases. Fig. 6 illustrates the
increase in solubility of β-carotene in SC-CO2 that occurs when the pressure of the system
Table 3
Compilation of literature data for lycopene solubility and yield in supercritical fluids from various sources
Yield (g/g raw Solubility Temp Pressure CO2 Flow Rate
SCF Solid material Cosolvent(s) material) ×106 (g/g solvent) ×106 (K) (MPa) (m3/h) ×103 Reference
CO2 tomato paste waste, CO2 2.2 – 308 30 2040.8 (40)
dried and ground 6.5 – 338 30 2040.8 (40)
CO2 + 5% ethanol 6.8 – 308 30 2040.8 (40)
15.1 – 338 30 2040.8 (40)
CO2 + 10% ethanol 4 – 308 30 2040.8 (40)
8.7 – 338 30 2040.8 (40)
CO2 + 15% ethanol 4.1 – 308 30 2040.8 (40)
6.2 – 328 30 2040.8 (40)
356
CO2 tomato seeds and skin CO2 0.6a – 305 13.8 0.15 (52)
2.1a – 323 48.3 0.15 (52)
4.6a – 359 34.5 0.15 (52)
CO2 tomato seeds and skin, CO2 124.2 – 323 27.6 3 (53)
dried and ground 644.1 – 353 27.5 3 (53)
CO2 purified lycopene from CO2 – 3.9 313 30.4 – (69)
tomato paste
– 16.1 323 28.1 – (69)
CO2 purified lycopene from CO2 – 20.1 333 40.3 – (69)
tomato paste
a
Values estimated from graph.
– not reported.
Table 4
Compilation of literature data for carotenoid solubility and yield in supercritical fluids from various sources
Yield (g/g raw Solubility (g/g Temp Pressure CO2 Flow Rate
SCF Solid material Cosolvent(s) material) ×106 solvent) ×106 (K) (MPa) (m3/h) ×103 Reference
CO2 microalga C. vulgaris, slightly crushed CO2 760 – 313 30 20.40 (42)
CO2 + soybean oil 840 – 313 30 20.40 (42)
CO2 + 5% ethanol 880 – 313 30 20.40 (42)
microalga C. vulgaris, completely CO2 2990 – 313 30 20.40 (42)
crushed CO2 + soybean oil 710 – 313 30 20.40 (42)
CO2 carrot, freeze dried and ground CO2 432.1 – 313 27.6 60 (55)
745.5 – 343 27.6 60 (55)
CO2 + 2.5% (w/w) canola oil 754.3 – 313 41.3 60 (55)
1647.7 – 343 55.1 60 (55)
357
CO2 + 5% (w/w) canola oil 989.8 – 313 27.6 60 (55)
1889.0 – 343 55.1 60 (55)
CO2 sweet potato tissue, fresh 43.6 – 311 41.4 840–1080 (58)
CO2 sweet potato tissue, freeze dried and 77.3 – 311 41.4 840–1080 (58)
ground (fine)
CO2 sweet potato tissue, freeze dried and 47.0 – 311 41.4 840–1080 (58)
ground (coarse)
CO2 microalga Nannochloropsis CO2 + Methanol 152 – 313 20 11.9 (59)
gaditana 180 – 323 50 11.9 (59)
252 – 333 50 11.9 (59)
CO2 paprika powder CO2 – 0.6 333 30 5102.0 (67)
– 3.0 333 30 5102.0 (67)
CO2 cyanobacterium, Synechoccus Species 0.7 – 313 20 6.1 (68)
2.4 – 333 50 6.1 (68)
358 Shi et al.
Table 5
Compilation of literature data for astaxanthin solubility and yield in
supercritical fluids from various sources
Solubility (g/g Temp Pressure
SCF Solid material Cosolvent(s) solvent) ×106 (K) (MPa) Reference
CO2 Astaxanthin standard, CO2 0.1 313 10 (69)
98% purity 5.7 323 31.5 (69)
16.3 333 38.7 (69)
Table 6
Compilation of literature data for capsanthin solubility and yield in

Yield
(g/g raw CO2
Cosolvent material) Temp Pressure density
SCF Solid material (s) ×106 (K) (MPa) (kg/m3) Reference
Capsanthin
CO2 red pepper flakes, CO2 750 313 32 922 (70)
ground and dried 910 313 54 1005 (70)
Capsanthin 5,6 epoxide
ground and dried 1330 313 43 969 (70)
Table 7
Compilation of literature data for capsorubin solubility and yield in
Yield
(g/g raw CO2
ground and dried 890 313 43 969 (70)
1100 313 54 1005 (70)
is increased. Corresponding to this trend, the amount of CO2 required reduces as the
extraction pressure increases. An increase in pressure results in an increase in fluid den-
sity, which might lead to a rapid increase in the solubility of the targeted component. The
solvating power of the supercritical fluid would increase and because of a decrease in the
diffusion coefficient at higher density, the interaction between the fluid and the matrix
Table 8
Compilation of literature data for cryptocapsin solubility and yield in
Yield
(g/g raw CO2
ground and dried 620 313 54 1005 (70)
Table 9
Compilation of literature data for β-cryptotoxanthin solubility and
yield in supercritical fluids from various sources
Yield
(g/g raw CO2
ground and dried 890 313 54 1005 (70)
Table 10
Compilation of literature data for lutein solubility and yield in
Yield
(g/g raw CO2
Solid Cosolvent material) Temp Pressure Extraction density
SCF material (s) ×106 (K) (MPa) time (h) (kg/m3) Reference
CO2 carrot, CO2 30.2 313 27.6 4 0.06 (55)
freeze 30.3 343 27.6 4 0.06 (55)
dried and
ground
CO2 CO2 + 2.5% 79.5 313 27.6 4 0.06 (55)
(w/w) 114.6 343 55.1 4 0.06 (55)
canola oil
CO2 CO2 + 5% 65.5 313 27.6 4 0.06 (55)
(w/w) 142.3 343 55.1 4 0.06 (55)
canola oil
360 Shi et al.
Table 11
Compilation of literature data for zeaxanthin solubility and yield in
Yield
(g/g raw CO2
ground and dried 2410 313 54 1005 (70)
1.8
1.6
1.4
β-Carotene (mg)
1.2
0.8
0.6
12 MPa
0.4 15 MPa
20 MPa
0.2
0
0 200 400 600 800 1000 1200
CO2 (g)
Figure 6. β-carotene extraction yields at various pressures and 323 K as a function of the amount of
carbon dioxide used in the extraction process. (Modified from Saldaña et al.(56) with permission
from Elsevier).
would be reduced.(35) Sabio et al.(33) noted that after a certain point, yield changes when
increase in the pressure/density was insignificant.
Results from Subra et al.(54) indicate that at lower pressures, the uncertainty of solu-
bility measurements increases. However, low solubility of the condensed phase, particu-
larly those of β-carotene, occurs at pressures close to the critical pressure of the solvent.
The errors may be larger at lower pressures because of the decreased absorbance.(46)
Discrepancies between data from the literature may be attributed to the different experi-
mental techniques used, as well as the assortment of carotenoids and CO2 purities applied
in the extraction processes.
The effect of pressure is enhanced by the addition of entrainers such as canola oil.(55)
Carotenoid yield data from an experiment conducted by Sun and Temelli(55) provided in
Table 4 demonstrated that the solubility of carotenoids increases as the pressure increases;
however, an entrainer will enhance this effect under the same experimental conditions.
The authors of the study hypothesized that interaction between the plant material matrix
and the canola oil led to increased carotenoid yields. They proposed that the solvent’s abil-
ity to diffuse through the matrix may have been facilitated by the canola oil, which may
have caused the cellular structures within the source material to swell and to release the
carotenoids from the matrix. The nonpolar nature of the SC-CO2 and the canola oil may
also influence the results. Finally, competition from the canola oil for adsorption sites with
the carotenoids may also enhance carotenoid release.(55)
Temperature. It is important to observe the temperature at which the targeted components

decompose, and to keep the parameters realistic for use in the food industry. For example,
Lycopene becomes unstable at 393°K; Ollanketo et al.(1) ensured that experimental condi-
tions did not exceed 383°K. Saldaña et al.(56) noted that isomerization of β-carotene may
not occur at temperatures less than 343°K, although it was observed at this temperature
after approximately 2 hr. Therefore, despite the fact that it may be tempting to perform the
extraction at a high temperature to increase the solubility of the targeted component, the
effect of the temperature and the extraction time should be evaluated in terms of degrada-
tion. The crystallinity of solids such as β-carotene is not well preserved under high tem-
peratures. However, this has an impact on the solubility because a crystalline solid has a
lower solubility than an amorphous solid because of the difference in free energy and a
relatively higher enthalpy of fusion.(45)
The effects of temperature are harder to assess than pressure; an increase in tempera-
ture leads to an augmentation in solute vapor pressure and a decrease in SCF density, but
the magnitude of the change in density becomes smaller at elevated temperatures.(57)
Spanos et al.(58) showed increased yield using SF-CO2 at lower temperatures when the
pressure was low (13.8 MPa); however, at high pressure (41.4 MPa), the opposite effect
was observed, in which an increase in temperature produced higher extraction yields.
Experimental data taken at an intermediate pressure (27.6 MPa) indicates that temperature
increases had no apparent effect.(58) This behavior may be explained by a complex balance
between the density of the solvent and the solute vapor pressure as the temperature is
increased.(58) A decrease in density would lead to a reduced yield; however, the increase in
vapor pressure of the pigments as the temperature increases should lead to higher
solubility.(58,59) For example, at the low pressure (13.8 MPa), it was suggested that the
increase in solute vapor pressure could not compensate the relatively large drop in solvent
density from the increase in temperature. The opposite effect may have occurred at high
pressures, in which the effect of the increase in solute vapor pressure overcame the rela-
tively small change in density when the temperature was increased. The intermediate pres-
sure would have a balance between the two.(58)
At a constant density, solubility increases a rise in temperature, due to the increase in
vapor pressure of the solid.(47) Fig. 7 shows the relative extraction of lycopene at varying
temperatures when the pressure and CO2 flow rate were kept constant. A similar relation-
ship was observed in work by Rozzi et al.(52) in Table 3. Experimental data from Hansen
et al.(45) suggest that the uncertainty of solubility measurements increase as the tempera-
ture decreases.
Cosolvents. Although the nature of CO2 drastically reduces or eliminates the solubility of
many polar molecules, this is easily remedied with the addition of polar entrainers. Modi-
fiers such as methanol increase the solubility of polar compounds but may also increase
the critical temperature of the solvent. This may be an issue for compounds that are
362 Shi et al.
100
90
80
Relative Recovery (%)
70
60°C
60
85ºC
50 110ºC
40
30
20
10
0
0 10 20 30 40 50 60 70 80
Extraction Time (min)
Figure 7. Relative recoveries of lycopene from tomato skins at a constant pressure of 40.5 MPa and
a CO2 flow rate of 1.5 mL/min. (Modified from Ollanketo et al.(1) with permission from Springer).
thermally labile, thus, entrainers must be used with caution. Another possible liability of
the addition of modifiers is product contamination. This may be solved with the addition
of a separation step subsequent to the extraction process.(45)
Several studies have been conducted to observe the effects of entrainers. Results from
Chandra and Nair(12) indicated that the addition of solvent modifiers to SC-CO2 increase
solvating power (Table 2 a,b). Modifiers were hexane and chloroform; chloroform had a
higher increase in solvating power. Chang and Randolph(36) observed that the solubility of
β-carotene increased with the addition of toluene. The highest solubility reported (Table 2b)
was more than nine times higher than the extraction without toluene under the same condi-
tions, thus showing a large β-carotene solubility enhancement factor. The influence of
various modifiers at a constant temperature, pressure, and solvent flow rate was studied by
Ollanketo et al.(1) Fig. 8 shows that the optimal results from this particular study were
obtained from the addition of acetone, which provided a relative recovery of 94% in
15 min, thus saving time, energy, and costs. In reality, however, ethanol is the only viable
modifier that may be used in large-scale food applications. Cygnarowicz et al.(60) also
reported that ethanol functioned as a more effective entrainer than methanol and methyl-
ene chloride. It appears modifiers that are miscible with water, such as acetone and metha-
nol, provide higher recoveries than those that are not, including hexane and
dichloromethane. However, a disadvantage of using ethanol as a co-solvent is the fact that
an additional step must be added to the process to remove it from the final product. This
procedure requires the use of heat, thus posing the risk of isomerization of the targeted
compound.(55)
One of the major advantages of SFE is its ability to produce nontoxic extracts. How-
ever, the additions of toxic organic solvents essentially negate this advantage. Natural
entrainers used in the extraction of carotenoids include vegetable oils and waxes. How-
ever, Sovová et al.(5) indicated that the entrainer effect of vegetable oil was not as great as
ethanol, with the increase in β-carotene solubility being four times smaller. The effect of
vegetable oil as a modifier is limited because of its low solubility in CO2.(5) Canola oil has
100
90
80
Relative Recovery (%)
70
60
50
40 Acetone
Methanol
30 Ethanol
Hexane
20 Dichloromethane
No Addition
10
0
0 10 20 30 40 50 60 70 80
Extraction Time (min)
Figure 8. Relative recoveries of lycopene from powdered tomato skins at 110°C, 400 atm, and a
CO2 flow rate of 1.5 mL/min with various modifiers. 100% relative recovery represents the best
recovery result. (Modified from Ollanketo et al.(1) with permission from Springer).
been suggested as a natural co-solvent, and it is highly soluble in SC-CO2 in comparison

to β-carotene, and results show that the carotenoid concentration nearly doubled from the
addition of canola oil. The effect of increasing the pressure was also heightened by this
modifier. Sun and Temelli(55) hypothesized that this effect may have occurred because of
interactions between the modifier and the solid material. Penetration of the oil into the
vegetable matrix may swell it, thus making it easier for the SC-CO2 to penetrate the
matrix. In addition, the oil may help release carotenoids in the matrix by loosening the cell
structures and increasing solute exposure.
Solvent Flow Rate and Density. In SFE extraction, the CO2 flow rate has an influence on
the extraction efficiency; when the flow rate is increased, the extraction rate also
increases. The amount of CO2 also affects the concentration of carotene in the extrac-
tion.(30) Because the intra-particle diffusion resistance is important, the extraction rate will be
a function of CO2 consumed; the higher the amount of supercritical gas used, the higher
the yield obtained.(30)
The amount of CO2 in contact with the sample indexes with an increase of flow rate.
The effect of various solvent flow rates on the carotenoid yield when the temperature,
pressure, and overall extraction time are kept constant.(55) The overlap of extraction curves
indicates equilibrium solubility. However, excessively high flow rates will produce unde-
sirable results because of a decrease in contact times between the solvent and the solute.
This may force the solvent to leave the system without reaching its solubility limit.(55)
High flow rates may also cause the sample to compact and restrict the fluid flow, thus
reducing the amount of solvent that comes in contact with the solute.(52) Baysal et al.(40)
noted that the recovery of lycopene at a CO2 flow rate of 8 kg/hr did not vary significantly
with a flow rate of 4 kg/hr. However, in the case of β-carotene, a flow rate of 4 kg/hr
364 Shi et al.
produced better results relative to 8 kg/hr. The component solubility and total extraction yield
are combination results of the interaction of solvent flow rate, pressure, and temperature.
As discussed in the Carotenoids section, there are three distinct regions in the extrac-
tion of natural products. By comparing the concentration of carotene extracted from
SC-CO2, and the amount of extract and how much CO2 that was used for the process, a
conclusion may be drawn that the largest amount of carotene is extracted in the constant
rate of mass transfer period.(30) Extraction process performed at relatively low CO2 densi-
ties (i.e., 0.25 g/mL) provided very low carotenoid yields. Higher densities resulted in
extracts that were richer in different carotenoids.(50)
An increase in the volume of CO2 used in the extraction process resulted in an increase
in extraction recovery up to a certain point. Results from Spanos et al.(58) showed a maxi-
mum carotenoid recovery increase of approximately 80% by SFE. Increasing the CO2 flow
rate improved the heat and mass transfer within the system, since the following fluid temper-
ature approached the wall temperature more quickly. The effect of solvent flow rate on mass
transfer rate and total yield in the constant extraction rate period is significant.
Composition of the Material. Discrepancies between extraction results published in the

literature may be attributed to the variability source materials. For example, an experiment
conducted using a synthetic carotenoid solution may not produce the same results as the
extraction of carotenoids from a natural product. The effect of the cellular structure in
plant products may hinder the extraction process,(55) although the results may be more
applicable to large-scale production scenarios. To overcome this cellular matrix effect,
modifiers may be used such as the aforementioned canola oil to expand the cells.
Extraction recovery results are affected by the size of the particles used for extraction.
Numerous experiments have shown that smaller particle sizes are ideal for extraction pro-
cesses, and the manner in which the solid material is crushed and powdered will also
affect the results.(1,42,55,58,61) The degree to which the material is crushed will determine
the amount of cells that are broken, which has a positive correlation with pigment recov-
ery. However, if the particle sizes are exceedingly small, channelling may occur, which
would lead to a reduction in extraction yield.(62) Only 40% lycopene recovery was
obtained from powdered tomato skins crushed with a household blender,(1) relative to the
amount achieved when sea sand was used to assist the grinding procedure. As is shown in
Fig. 9, the degree of material crushing characterizes the amount of carotenoids extracted.
Sun and Temelli(55) noted that the optimal range of particle sizes was found to be between
0.25–0.5 mm when examining the yields of lutein, β-carotene, and α-carotene. Gouveia
et al.(42) studied the effects of slight, moderate, and complete crushing, which yielded
20%, 40%, and 65% carotenoid recovery, respectively, which was relative to the amount
extracted with acetone. These results support the theory of solute diffusion in particles; the
corresponding data are in Table 4.
The behavior of the curves in Fig. 9 can be explained by the lipids that surround the
particles of the microalgae. The CO2 extracts these lipids prior to penetrating the porous
structure of the material to reach the carotenoids that are possibly bound to solid cell frag-
ments. Thus, the initial recoveries of each curve (Fig. 9) decrease with the degree of crush-
ing. The carotenes are extracted after they are dissolved in CO2. A similar proposal
concerning lipids being dissolved prior to carotenoids was made by de França et al.(30) in
the extraction of buriti fruit. Their results indicated that the bulk of the carotenoids were
obtained during the diffusion-controlled period of the extraction, which occurs after the
typical constant extraction rate period. The results from their experiment yielded a curve
with similar behavior as in Fig. 9.
70
60
50
% Recovery
40
30
Slightly - Degree 1
Fair - Degree 2
20
Complete - Degree 3
10
0
0 20 40 60 80 100 120 140
CO2 (g/galga)
Figure 9. The recovery of carotenoids from various degrees of crushing of microalgae Chlorella
vulgaris samples at 313 K, 30 MPa, and a solvent flow rate of 0.0204m3/h. Degree 1: manually
crushed; Degree 2: manually crushed mixed with dry ice; Degree 3: crushed with a disk vibratory
mill. (Modified from Gouveia et al.(42) with permission from Elsevier).
The extraction process is hindered by large particle sizes because of the distance the
solute must travel from the inside of the particle to the surface. By reducing the size of the
particles, components such as carotenoids have less distance to travel. Thus, the collective
amount of surface area that the solvent is in contact with is increased, which is important
during the initial stages of extraction.(1) However, the structure of the component in ques-
tion will influence the effect of the particle size; for example, compounds such as the car-
otenoid lutein are relatively unaffected by varying the particle size. This may be attributed
to its tendency to bind to cell structure components, therefore making it difficult to extract,
regardless of particle size.(55) However, for certain processes, it is important to be cautious
of the degree of crushing. Gouveia et al.(42) found that samples that have been extremely
crushed may not be affected by the addition of entrainers. This indicated that the maxi-
mum amount of carotenoids that could possibly be extracted were available for supercriti-
cal extraction. Methods that may be applied to reduce particle sizes include manually with
dry ice,(42) using disk vibratory mills and blenders, and mixing the sample with sea sand.(1)
The molecular composition of the solid material should also be taken into consider-
ation. Results from extractions of carotenoids from microalgae may encompass varia-
tions in the yields because of the thick cellular wall that leads to great mass transfer
resistance.(59)
Storage Conditions. The concentration of carotenoids in biological materials degrades

over time, which is influenced by the matrix. In addition, the manner in which the samples
are stored influences the degradation, and factors such as particle sizes, temperatures, and
moisture must be considered. Decrease in concentration is faster with smaller particles
(i.e., tomato skin powder versus crushed tomatoes). Light does not have a significant
effect.(1) Evidence of autocatalytic reactions were also found when tomato pulp that was
stored in a frozen state under vacuum experienced lycopene loss(53); the nitrogen
366 Shi et al.
atmosphere has relatively little effect on lycopene stability.(1) Additives such as antioxi-
dants or stabilizers should be considered when using commercial tomato powders in
extraction procedures, since they may yield high lycopene concentration, despite long
storage periods.
Extraction Times. When optimizing the extraction conditions, the extraction time of the
process is an important parameter. Shortening of extraction time while maintaining maxi-
mum extraction recovery is important from the cost point of view. In the extraction of
lycopene in SC-CO2, Baysal et al.(40) found that the highest carotene yield was obtained at
an extraction time of 2 hr, as opposed to 1- or 3-hr periods. The duration of a 1-hr extrac-
tion may not suffice for the maximum amount of carotenoids to dissolve in the solvent,
while a period of 3 hr may increase the occurrence of degradation. The duration and the
intensity of thermal processing are directly correlated to the degree of isomerization and
degradation of the targeted compounds.(63) Therefore, to minimize the degradation effect,

it is advisable to reduce the extraction time as much as possible.(50) In addition, optimizing
extraction conditions toward the shortest extraction time possible with the maximum
extraction recovery is ideal from the point of view of the quality of extract and processing
cost. This may be optimized by varying the sample size, dynamic extraction time, temper-
ature, pressure, and other processing parameters that affect solute solubility and final
extraction yield. Based on the combination effects of pressure, temperature, extraction
time, and co-solvents on solubility and extraction yield, the duration of extraction time
decreased with increased pressure and temperature.(64)
Multiple extraction stages may be used to further increase the concentration of caro-
tenoids and other minor constituents. Chuang and Brunner(34) conducted a three-stage
enrichment process that involved three transesterification steps. The first step showed a
13-fold enrichment of β-carotene, it became ten times as concentrated from the second
step, and after the three extraction steps, an enrichment of 200-fold was obtained for caro-
tenoids. In cases in which the target components extracted are easily accessible at the sur-
face of material particles, there is no reason to extend extraction up to the end because of
the drastic increase in the solvent compression cost of increasing the yield.
Water Content of the Material. Approximately 80–90% of the total weight of plant
materials is attributed to water content. However, water content influences the effi-
cacy of SC-CO2 extraction processes. Therefore, the drying process is an important
step in SFE.(65) A drying step is implemented prior to the extraction process to
increase efficiency. Many compounds such as carotenoids are sensitive to light, heat,
and oxygen; therefore freeze-drying is an effective method for removing moisture
from samples while avoiding degradation. A disadvantage to this process is the cost;
therefore, optimizing the level of drying may improve the efficiency of the process.(55)
Alternatives to freeze-drying include vacuum drying,(55) air drying,(66) and drum dry-
ing.(58) However, the drying process should be carefully chosen to minimize any neg-
ative effect on the targeted components, material matrix, or any other factors in the
extraction process. Oven drying of raw material by Spanos et al.(58) provided a higher
yield, but always oxidative degeneration and case hardening. In the case of drum dry-
ing, severe case hardening prevented the extraction of carotenoids. The best pretreat-
ment method was freeze drying.(58)
Depending on the polarity of the compound, the initial moisture content may improve
or impede the yield of carotenoids in SFE. Nonpolar compounds such as α-carotene and
β-carotene produce smaller yields with higher moisture content(44,55); however, yields of
polar compounds such as lutein increase with moisture.(55) Possible effects of water
include an increase in distance that carotenoids must travel to reach the solvent and swell-
ing of the cell matrix, which have negative and positive effects on the process, respec-
tively.(55) Data indicate that the presence of water aided in the extraction of carotenoids,
particularly in the beginning of the process. The total carotene recovery from materials
that were previously dried was quite similar to that from starting material, which did not
undergo a drying process.(67)
Conclusion
Carotenoids are used in the pharmaceutical, food, and cosmetic industries to enhance
health benefits, physical attributes, and to provide a natural alternative to synthetic dyes
for various consumer products. Large-scale supercritical fluid extraction has become an
ideal candidate for the extraction of particular components. SFE with solvents such as CO2
offers a safe and nontoxic alternative to traditional extraction methods that use organic
solvents, and may be used to extract thermally labile compounds.
There are many factors that influence the solubility of biomolecules in supercritical
fluids. The density, pressure, and temperature of the solvent have been noted to have great
impact on the results of the extraction process. Other factors include the particle size,
molecular structure, and polarity of the targeted carotenoid. The state and composition of
the raw material has an effect because of matrix complexities that include lipid, caro-
tenoid, and carbohydrate fractions, as well as moisture content and storage conditions. By
understanding the effect of the parameters that influence the extraction process, conditions
may be set to optimize yield and cost efficiency.
When determining the parameters that should be used to maximize the carotenoid
yield and solubility, many researchers attempted to use conditions that may be applica-
ble in large-scale applications. For example, nontoxic cosolvents and modifiers would
be acceptable for food processing; therefore, a number of researchers opted to use
canola oil, ethanol, or simply no additional solvents at all. Although a high temperature
in the extraction process generally increases the solubility of components in supercriti-
cal fluids, the conditions at which thermally labile targeted compounds are negatively
affected should be considered. The intensity and the length of heat processing affect the
degree of isomerization; therefore, ideally, the extraction time and temperature should
be minimized. Minimizing such conditions also leads to a more economically viable
process.
Excessively high flow rates may reduce the contact time between the solute and the
solvent and restrict the fluid flow in the sample if it becomes compacted. The optimal flow
rate appears to vary with the targeted molecule; relatively high flow rates having a nega-
tive effect on some components, yet no effect on others. Higher pressure increases caro-
tenoid yields; however, the distribution of carotenoid, obtained also varies with pressure.
Lycopene results are better at the end of the extraction, whereas high β-carotene content is
obtained near the beginning. However, after a certain point, the solubility is not signifi-
cantly affected by the increase in pressure.
The nature of the material used as a source of carotenoids governs the availability of
the compounds for the extraction process. The presence of other components such as lip-
ids may impede the process or elevate costs because of an elongated extraction time. The
manner in which the material is stored also affects the results, since carotenoids degrade
over time, the rate of which depending on storage temperature, particle size, and the pres-
ence of additional antioxidants or stabilizers.
368 Shi et al.
References
1. Ollanketo, M.; Hartonen, K.; Riekkola, M.L.; Holm, Y.; Hiltunen, R. Supercritical Carbon
Dioxide Extraction of Lycopene in Tomato Skins. European Food Research and Technology
2001, 212, 561–565.
2. Mittal, G.S. Food Biotechnology: Techniques and Applications; Lancaster, PA: Technomic
Publishing Company; 1992.
3. Hartono, R.; Mansoori, G.A.; Suwono, A. Prediction of Solubility of Biomolecules in Supercrit-
ical Solvents. Chemical Engineering Science 2001, 56, 6949–6958.
4. Mukhopadhyay, M. Natural Extracts Using Supercritical Carbon Dioxide; Boca Raton, FL:
CRC Press; 2000.
5. Sovová, H.; Stateva, R.P.; Babushka, A.A. Solubility of β-Carotene in Supercritical CO2 and the
Effect of Entrainers. The Journal of Supercritical Fluids 2001, 21, 195–203.
6. Kurnik, R.T.; Reid, R.C. Solubility of Solid Mixtures in Supercritical Fluids. Fluid Phase Equi-
libria 1982, 8, 93–105.

7. Škerget, M.; Knez, Ž.; Habulin, M. Solubility of β-carotene and Oleic Acid in Dense CO2 and
Data Correlation by a Density Based Model. Fluid Phase Equilibria 1995, 109, 131–138.
8. Jay, A.J.; Steytler, D.C. Nearcritical Fluids as Solvents for β-carotene. The Journal of Supercrit-
ical Fluids 1992, 5, 274–282.
9. Jarén-Galán, M.; Nienaber, U.; Schwartz, S.J. Paprika (Capsicum annum) Oleoresin Extrac-
tion with Supercritical Carbon Dioxide. Journal of Agricultural Food Chemistry 1999, 47,
3558–3564.
10. Mendes, R.L.; Nobre, B.P.; Coelho, J.P.; Palavra, A.F. Solubility of β-carotene in Supercritical
Carbon Dioxide and Ethane. The Journal of Supercritical Fluids 1999, 16, 99–106.
11. Ambrogi, A.; Cardarelli, D.A.; Eggers, R. Separation of Natural Colorants Using a Combined High
Pressure Extraction-Absorption Process. Latin American Applied Research 2003, 33, 323–326.
12. Chandra, A.; Nair, M.G. Supercritical Fluid Carbon Dioxide Extraction of α- and β-Carotene
from Carrot (Daucus carota L.). Phytochemical Analysis 1997, 8, 244–246.
13. Ploeger, J.M.; Bielenberg, P.A.; Lachance, R.P.; Tester, J.W. Co-oxidation of Methylphosphonic
Acid and Ethanol in Supercritical Water. The Journal of Supercritical Fluids 2006, 39, 233–239.
14. Savage, P.E.; Gopalan, S.; Mizan, T.I.; Martino, C.J.; Brock, E.E. Reactions at Supercritical
Conditions, Applications and Fundamentals. AIChE Journal 1995, 41, 1723–1778.
15. Thomason, T.B.; Hong, G.T.; Swallow, J.W.; Killilea, W.R. The MODAR Supercritical Water
Oxidation Process. In H.M. Freeman, (Ed.), Innovative Hazardous Waste Treatment Technology
Series, Thermal Processes; Lancaster, PA: Technomic Publishing; 1990, 31–32.
16. Cacace. J.E.; Mazza, G. Pressurized Low Polarity Water Extraction of Biologically Active
Compounds from Plant Products. In J. Shi (Ed.), Functional Food and Nutraceuticals: Process-
ing and Technologies; Boca Raton, FL; CRC Press 2006: 135–155.
17. Clifford, A.A.; Basile, A.; Al-Saidi, S.H.R. A Comparison of the Extraction of Clove Buds with
Supercritical Carbon Dioxide and Superheated Water. Fresenius’ Journal of Analytical Chemis-
try 1999, 364, 635–637.
18. Warabi, Y.; Kusdiana, D.; Saka, S. Biodiesel Fuel from Vegetable Oil by Various Supercritical
Alcohols. Applied Biochemistry and Biotechnology, 2004, 115, 793–802.
19. Demirbas, A. Liquefaction of Olive Husk by Supercritical Fluid Extraction. Energy Conversion
and Management 2000, 41, 1875–1883.
20. Zhang, Y.; Yang, J.; Yu, Y.X.; Li, Y.G. Structural and Hydrogen Bond Analysis for Supercritical
Ethanol: A Molecular Simulation Study. The Journal of Supercritical Fluids 2005, 36, 145–153.
21. Kamitanaka, T.; Matsuda, T.; Harada, T. Reduction of Acetophenone Using Supercritical 2-
Propanol, the Substituent Effect and the Deuterium Kinetic Isotope Effect. Tetrahedron Letters
2003, 44, 4551–4553.
22. Mohamed, R.S.; Saldaña, M.D.A.; Socantaype, F.H.; Kieckbusch, T.G. Reduction in the
Cholesterol Content of Butter Oil Using Supercritical Ethane Extraction and Adsorption on
Alumina. The Journal of Supercritical Fluids 2000, 16, 225–233.
23. Raeissi, S.; Peters, C.J. Experimental Determination of High-Pressure Phase Equilibria of the
Ternary System Carbon Dioxide + Limonene + Linalool. The Journal of Supercritical Fluids
2005, 35, 10–17.
24. Olmstead, J.A.; Williams, G.M. Chemistry, Third Edition; Hoboken, NJ: John Wiley & Sons;
2002.
25. Hansen, C.M. Hansen Solubility Parameters; Boca Raton, FL: CRC Press; 2000.
26. Shi, J.; Zhou, X. Solubility of Food Components and Product Recovery in the Supercritical
Fluid Separation Process. In J. Shi, (Ed.) Functional Food and Nutraceuticals, Processing &
Technologies; Boca Raton, FL: CRC Press; 2006, 45–73.
27. Schmitt, W.J.; Reid, R.C. Solubility of Monofunctional Organic Solids in Chemically Diverse
Supercritical Fluids. Journal of Chemical and Engineering Data 1986, 31, 204–212.
28. Dandge, D.K.; Heller, J.P.; Wilson, K.V. Structure Solubility Correlations, Organic Compounds
and Dense Carbon Dioxide Binary Systems. Industrial and Engineering Chemistry Product
Research and Development 1985, 24, 162–166.
29. Bulley, N.R.; Fattory, M.; Meisen, A.; Moyls, S. Supercritical Fluid Extraction of Vegetable Oil
Seeds. Journal of American Oil Chemistry Society 1984, 61, 1362–1365.
30. de França, L.F.; Reber, G.; Meireles, M.A.A.; Machado, N.T.; Brunner, G. Supercritical Extrac-
tion of Carotenoids and Lipids from Buriti (Maura flexuosa), a Fruit from the Amazon Region.
The Journal of Supercritical Fluids 1999, 14, 247–256.
31. Ferreira, S.R.S.; Meireles, M.A.A.; Cabral, F.A. Extraction of Essential Oil of Black Pepper
with Liquid Carbon Dioxide. Journal of Food Engineering 1993, 20, 121–133.
32. Sovová, H. Rate of the Vegetable Oil Extraction with Supercritical CO2—I. Modelling of
Extraction Curves. Chemical Engineering Science 1994, 4, 409–414.
33. Sabio, E.; Lozano, M.; Montero de Espinosa, V.; Mendes, R.L.; Pereira, A.P.; Palavra, A.F.;
Coelho, J.A. Lycopene and β-carotene Extraction from Tomato Processing Waste Using Super-
critical CO2. Industrial and Engineering Chemistry Research 2003, 42, 6641–6646.
34. Chuang, M.H.; Brunner, G. Concentration of Minor Components in Crude Palm Oil. The Jour-
nal of Supercritical Fluids 2006, 37, 151–156.
35. Gordon, H.T.; Bauernfeind, J.C. Carotenoids as Food Colorants. Critical Reviews in Food Sci-
ence and Nutrition 1982, 18, 59–97.
36. Chang, C.J.; Randolph, A.D. Precipitation of Microsize Organic Particles from Supercritical
Fluids. AIChE Journal 1989, 35, 1879–1882.
37. Sweeney, J.M.; Marsh, A.C. Liver Storage of Vitamin A in Rats Fed with Carotene Stereoiso-
mers. Journal of Nutrition 1973, 103, 20–25.
38. Chandler, L.A.; Schwartz, S.J. Isomerization and Losses of Trans-β-Carotene in Sweet Potatoes
as Affected by Processing Treatments. Journal of Food Chemistry 1988, 36, 129–133.
39. Boskovic, M. Fate of Lycopene in Dehydrated Tomato Products, Carotenoid Isomerization in
Food Systems. Journal of Food Science 1979, 44, 84–86.
40. Baysal, T.; Ersus, S.; Starmans, D.A.J. Supercritical CO2 Extraction of β-Carotene and
Lycopene from Tomato Paste Waste. Journal of Agricultural and Food Chemistry 2000, 48,
5507–5511.
41. Barth, M.M.; Zhou, C.; Kute, K.M. Rosenthal, G.A. Determination of Optimum Conditions for
Supercritical Fluid Extraction of Carotenoids from Carrot (Daucus carota L.) Tissue. Journal of
Agricultural Food Chemistry 1995, 43, 2876–2878.
42. Gouveia, L.; Nobre, B.P.; Marcelo, F.M.; Mrejen, S.; Cardoso, M.T.; Palavra, A.F.; Mendes,
R.L. Functional Food Oil Coloured by Pigments Extracted from Microalgae with Supercritical
CO2. Food Chemistry, 2007, 101(2), 717–723.
43. Hejazi, M.A.; de Lamarliere, C.; Rocha, J.M.S.; Vermuë, M.; Tramper, J. Selective Extraction
of Carotenoids from Microalga Dunaliella salina with Retention of Viability. Biotechnology
and Bioengineering 2002, 79, 29–36.
44. Weathers, R.M.; Beckholt, D.A.; Lavella, A.L.; Danielson, N.D. Comparison of Acetals as in
situ Modifiers for the Supercritical Fluid Extraction of β-carotene from Paprika with Carbon
Dioxide. Journal of Liquid Chromatography and Related Technologies 1999, 22, 241–252.
370 Shi et al.
45. Hansen, B.N.; Harvey, A.H.; Coelho, J.A.P.; Palavra, A.M.F.; Bruno, T.J. Solubility of Capsaicin
and β-carotene in Supercritical Carbon Dioxide and in Halocarbons. Journal of Chemical and
Engineering Data 2001, 46, 1054–1058.
46. Sakaki, K. Solubility of β-carotene in Dense Carbon Dioxide and Nitrous Oxide from 308 to
323 K and from 9.6 to 30 MPa. Journal of Chemical and Engineering Data 1992, 37, 249–251.
47. Johannsen, M.; Brunner, G. Solubilities of the Fat-Soluble Vitamins A, D, E, and K in Super-
critical Carbon Dioxide. Journal of Chemical and Engineering Data 1997, 42, 106–111.
48. Jay, A.J.; Steytler, D.C.; Knights M. Spectrophotometric Studies of Food Colors in Near-
Critical Carbon Dioxide. The Journal of Supercritical Fluids 1991, 4, 131–141.
49. Cocero, M.J.; González, S.; Pérez, S.; Alonso, E. Supercritical Extraction of unsaturated Prod-
ucts. Degradation of β-carotene in Supercritical Extraction Processes. The Journal of Supercriti-
cal Fluids 2000, 19, 39–44.
50. Gómez-Prieto, M.S.; Caja, M.M.; Herraiz, M.; Santa-María, G. Supercritical Fluid Extraction of
All-Trans Lycopene from Tomato. Journal of Agricultural and Food Chemistry 2003, 51, 3–7.
51. Miguel, F.; Martín, A.; Gamse, T.; Cocero, M.J. Supercritical Anti Solvent Precipitation of
Lycopene Effect of the Operating Parameters. The Journal of Supercritical Fluids 2006, 36,
225–235.
52. Rozzi, N.L.; Singh, R.K.; Vierling, R.A.; Watkins, B.A. Supercritical Fluid Extraction of Lyco-
pene from Tomato Processing Byproducts. Journal of Agricultural and Food Chemistry 2002,
50, 2638–2643.
53. Cadoni, E.; De Giorgi, M.R.; Medda, E.; Poma, G. Supercritical CO2 Extraction of Lycopene
and β-carotene from Ripe Tomatoes. Dyes and Pigments 2000, 44, 27–32.
54. Subra, P.; Castellani, S.; Ksibi, H.; Garrabos, Y. Contribution to the Determination of the Solu-
bility of β-carotene in Supercritical Carbon Dioxide and Nitrous Oxide, Experimental Data and
Modelling. Fluid Phase Equilibria 1997, 131, 269–286.
55. Sun, M.; Temelli, F. Supercritical Carbon Dioxide Extraction of Carotenoids from Carrot Using
Canola Oil as a Continuous Co-solvent. The Journal of Supercritical Fluids 2006, 37, 397–408.
56. Saldaña, M.D.A.; Sun, L.; Guigard, S.E.; Temelli, F. Comparison of the Solubility of β-carotene
in Supercritical CO2 Based on a Binary and a Multicomponent Complex System. The Journal of
Supercritical Fluids 2006, 37, 342–349.
57. Marentis, R.T. Steps to Developing a Commercial Supercritical Carbon Dioxide Processing
Plant. In B.A. Charpentier and M.R. Sevenants, (Ed.), Supercritical Fluid Extraction and Chro-
matography; American Chemical Society, Symposium Series; 1988: 127–143.
58. Spanos, G.A.; Chen, H.; Schwartz, S.J. Supercritical CO2 Extraction of β-carotene from Sweet
Potatoes. Journal of Food Science 1993, 58, 817–820.
59. Macías-Sánchez, M.D.; Mantell, C.; Rodríguez, M. Martínez de la Ossa, E.; Lubián, L.M.;
Montero, O. Supercritical Fluid Extraction of Carotenoids and Chlorophyll a from Nannochlo-
ropsis gaditana. Journal of Food Engineering 2005, 66, 245–251.
60. Cygnarowicz, M.L.; Maxwell, R.J.; Seider, W.D. Equilibrium solubilites of β-Carotene in
Supercritical Carbon Dioxide. Fluid Phase Equilibria 1990, 59, 57–71.
61. Ferreira, S.R.S.; Meireles, M.A.A. Modeling the Supercritical Fluid Extraction of Black Pepper
(Piper nigrum L.) Essential Oil. Journal of Food Engineering 2002, 54, 263–269.
62. Ziémons, E.; Goffin, E.; Lejeune, R.; Proença da Cunha, A.; Angenot, L.; Thunus, L. Supercrit-
ical Carbon Dioxide Extraction of Tagitinin C from Tithonia diversifolia. The Journal of Super-
critical Fluids 2005, 33, 53–59.
63. Schierle, J.; Bretzel, W.; Bühler, I.; Faccin, N.; Hess, D.; Steiner, K.; Schüep, W. Content and
Isomeric Ratio of Lycopene in Food and Human Blood Plasma. Food Chemistry 1997, 59, 459–465.
64. Pól, J.; Hyötyläinen, T.; Ranta-Aho, O.; Riekkola, M. Determination of Lycopene in Food by
On-line SFE Coupled to HPLC Using a Single Monolithic Column for Trapping and Separation.
Journal of Chromatography A 2004, 1052, 25–31.
65. Hopper, M.L.; King, J.W. Enhanced Supercritical Fluid Carbon Dioxide Extraction of Pesti-
cides from Foods Using Palletized Diatomaceous Earth. Association of Official Analytical
Chemists 1991, 74, 661–666.
66. Sun, L.; Rezaei, K.A.; Temelli, F.; Ooraikul, B. Supercritical Fluid Extraction of Alkylamides
from Echinacea augustifolia. Journal of Agricultural Food Chemistry 2002, 50, 3947–3953.
67. Ambrogi, A.; Cardarelli, D.A.; Eggers, R. Fractional Extraction of Paprika Using Supercritical
Carbon Dioxide and On-line Determination of Carotenoids. Journal of Food Science 2002, 67,
3263–3241.
68. Montero, O.; Macías-Sánchez, M.D.; Lama, C.M.; Lubían, L.M.; Mantell, C.; Rodríguez, M.;
de la Ossa, E. Supercritical CO2 Extraction of β-carotene from a Marine Strain of the Cyanobac-
terium Synechoccus Species. Journal of Agricultural and Food Chemistry 2005, 53, 9701–9707.
69. de la Fuente, J.C.; Oyarzún, B.; Quezada, N.; del Valle, J.M. Solubility of Carotenoid Pigments
(Lycopene and Astaxanthin) in Supercritical Carbon Dioxide. Fluid Phase Equilibria 2006; 247
(1–2), 90–95.
70. Uquiche, E.; del Valle, J.M.; Ortiz, J. Supercritical Carbon Dioxide Extraction of Red Pepper
(Capsicum annum L.) Oleoresin. Journal of Food Engineering 2004, 65, 55–66.
71. Gnayfeed, M.H.; Daood, H.G.; Illés, V.; Biacs, P.A. Supercritical CO2 and Subcritical Propane
Extraction of Pungent Paprika and Quantification of Carotenoids, Tocopherols and Capsaicinoids.

Journal of Agricultural and Food Chemistry 2001, 49, 2761–2766.
72. Kraska, T.; Leonhard, K.O.; Tuma, D.; Schneider, G.M. Correlation and Solubility of Low-
volatile Organic Compounds in Near- and Supercritical Fluids. Part I, Applications to Adaman-
tine and β-carotene. The Journal of Supercritical Fluids 2002, 23, 209–224.
73. Marshall, N. Division scientifique of L’Air Liquide. In Gas Encyclopedia; Amsterdam:
Elsevier; 1976.
74. Tuma, D.; Schneider, G.M. Determination of the Solubilities of Dyestuffs in Near- and Supercriti-
cal Fluids by a Static Method up to 180 MPa. Fluid Phase Equilibria 1999, 158–160, 743–757.
75. Poling, B.E.; Prausnitz, J.M.; O’Connell, J.P. The Properties of Gases and Liquids. 5th edition;
New York: McGraw-Hill; 2000.

Food Reviews International

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Food Reviews International

Uploaded by

Copyright:

Available Formats

This article was downloaded by: [Pennsylvania State University]

On: 28 April 2013, At: 22:29

Food Reviews International

Solubility of Carotenoids in Supercritical

To link to this article: http://dx.doi.org/10.1080/87559120701593806

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions

Solubility of Carotenoids in Supercritical CO2

JOHN SHI1, GAURI MITTAL2, ERIN KIM2 AND

SOPHIA JUN XUE1

Keywords cartenoids, extraction, supercritical fluid, solubility

Supercritical Fluid Extraction

Common Supercritical Fluids Used in Supercritical Fluid Extraction

Figure 1. Typical experimental apparatus used to measure solubilities in supercritical fluids.

Carbon Dioxide. Carbon dioxide is a common solvent because it is nontoxic, inexpen-

be solved through the addition of a small amount of polar modifiers.(1)

Triple Gas Phase

Alcohol. The literature on supercritical alcohol extraction is relatively limited. Supercriti-

Solubility of Carotenoids in Supercritical Fluids

Properties of Targeted Components in Supercritical Fluid Extraction

Figure 3. Structure of β-carotene.

extractability; however, the existence of polar functional groups impedes solubilitation.(26)

ability to dissolve components of similar volatility, despite dissimilar molecular organiza-

Typical Behavior of a Solid Solute in a Supercritical Solvent

Carotene. β-carotene (C40H56) is a relatively nonvolatile compound,(36) has no functional

CO2 + 10% ethanol 193a – 303 3 – (41)

Figure 5. Structure of lycopene.

Factors Affecting the Solubility of Carotenoids in SFE

Pressure. An increase in pressure at a constant temperature increases the solvating power

Compilation of literature data for capsanthin solubility and yield in

Temperature. It is important to observe the temperature at which the targeted components

been suggested as a natural co-solvent, and it is highly soluble in SC-CO2 in comparison

Composition of the Material. Discrepancies between extraction results published in the

Storage Conditions. The concentration of carotenoids in biological materials degrades

degradation of the targeted compounds.(63) Therefore, to minimize the degradation effect,

libria 1982, 8, 93–105.

Extraction of Pungent Paprika and Quantification of Carotenoids, Tocopherols and Capsaicinoids.

You might also like